CN111333854B - Super-hydrophobic porous coordination polymer based on partial fluoro organic ligand and preparation method and application thereof - Google Patents
Super-hydrophobic porous coordination polymer based on partial fluoro organic ligand and preparation method and application thereof Download PDFInfo
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- CN111333854B CN111333854B CN202010250087.3A CN202010250087A CN111333854B CN 111333854 B CN111333854 B CN 111333854B CN 202010250087 A CN202010250087 A CN 202010250087A CN 111333854 B CN111333854 B CN 111333854B
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- 239000013259 porous coordination polymer Substances 0.000 title claims abstract description 75
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000013110 organic ligand Substances 0.000 title claims abstract description 17
- 125000001153 fluoro group Chemical group F* 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- -1 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anions Chemical class 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims description 48
- 239000003446 ligand Substances 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- XCMFMABSVYLASO-UHFFFAOYSA-N 5-ethyl-3-(trifluoromethyl)-1h-1,2,4-triazole Chemical compound CCC1=NC(C(F)(F)F)=NN1 XCMFMABSVYLASO-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000001555 benzenes Chemical class 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- WTFXJFJYEJZMFO-UHFFFAOYSA-N propamidine Chemical compound C1=CC(C(=N)N)=CC=C1OCCCOC1=CC=C(C(N)=N)C=C1 WTFXJFJYEJZMFO-UHFFFAOYSA-N 0.000 claims description 5
- 229960003761 propamidine Drugs 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 43
- 239000013078 crystal Substances 0.000 abstract description 22
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 101150093988 maf-2 gene Proteins 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000523 sample Substances 0.000 description 18
- 230000002209 hydrophobic effect Effects 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013256 coordination polymer Substances 0.000 description 5
- 229920001795 coordination polymer Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NIGUTEXYIRYTPY-UHFFFAOYSA-N 3,5-bis(trifluoromethyl)-1h-1,2,4-triazole Chemical compound FC(F)(F)C1=NN=C(C(F)(F)F)N1 NIGUTEXYIRYTPY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 229940078552 o-xylene Drugs 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000005464 sample preparation method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UGERGYDWQOPISO-UHFFFAOYSA-N 3,5-diethyl-1h-1,2,4-triazole Chemical compound CCC1=NNC(CC)=N1 UGERGYDWQOPISO-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
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- 238000001953 recrystallisation Methods 0.000 description 2
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- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 210000002777 columnar cell Anatomy 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
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- 239000012071 phase Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- DFWRZHZPJJAJMX-UHFFFAOYSA-N propanimidamide;hydrochloride Chemical compound Cl.CCC(N)=N DFWRZHZPJJAJMX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
The invention discloses a super-hydrophobic porous coordination polymer based on a partial fluoro organic ligand, and a preparation method and application thereof, wherein the super-hydrophobic porous coordination polymer with a three-dimensional structure is formed by assembling all nitrogen atoms of 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anions and silver ions or monovalent copper ions after coordination, and the super-hydrophobic porous coordination polymer is respectively named as MAF-9 and MAF-2F. The preparation method of the super-hydrophobic porous coordination polymer is simple, the single crystal and powder preparation methods are suitable for occasions with different sample demands, and the prepared super-hydrophobic porous coordination polymer can adsorb equivalent amounts of benzene series, methanol, ethanol and other organic vapor at room temperature, does not adsorb water at all, can be used for separating volatile organic matters from water, and has good thermal stability and chemical stability.
Description
Technical Field
The invention relates to the technical field of super-hydrophobic porous materials, in particular to a super-hydrophobic porous coordination polymer based on a part of fluorinated organic ligand and a preparation method and application thereof.
Background
Most porous materials are hydrophilic, and few are hydrophobic. Hydrophobic porous materials are particularly useful not only in oil-water separation, self-cleaning surfaces, heterogeneous catalysis of gas adsorption, etc., but also they have anomalous gas adsorption selectivity and can be used to achieve efficient gas separation. And thanks to the non-hydrophilic character, the gas sensing and adsorptive separation/storage properties of hydrophobic porous materials can be substantially unaffected by the wide presence of water vapor in the environment (humid conditions). However, there are few reports of porous materials having high hydrophobicity, particularly superhydrophobicity. Of the tens of thousands of MOF materials, only about 100 are hydrophobic, while less than 10 are superhydrophobic.
FMOF-1([Ag(bftz)]Namely FMOF-1, represented by Hbftz as 3, 5-bis-trifluoromethyl-1, 2, 4-triazole) is an example of a classical metal-organic framework porous coordination polymer based on perfluorinated substituted organic ligands (C Yang, X Wang, MA Omary. fluoro metal-organic frameworks for high-sensitivity gas adsorption, Journal of the American chemical.2007,129, 15454). It can adsorb benzene series and various alkane organic solvents, but does not adsorb water at all, and the water contact angle reaches 158 degrees, so that it is a super-hydrophobic porous material. It can also capture CO by adsorption at high pressure2CO under humid conditions thanks to the hydrophobicity of the material2The adsorption performance is substantially unaffected by water vapor. In addition, FMOF-1 may exhibit interesting structural changes during adsorption of nitrogen or temperature swing. Although FMOF-1 has good properties and potential application value, the synthesis of 3, 5-bis (trifluoromethyl) -1,2, 4-triazole serving as a ligand is difficult, 6 steps of reactions including condensation, halogenation, amination and ring closure are needed to obtain the FMOF-1, the FMOF-1 and the triazole can be synthesized by volatilization and recrystallization in various organic solvents.
[ Cu (detz) ] (MAF-2; Hdetz ═ 3, 5-diethyl-1, 2, 4-triazole) (J. -P. Zhang, X. -M. Chen. Exceptional frame flexibility and absorption detector of a multi functional pore three salt frame. journal of the American Chemical society.2008,130,6010) is an example of a well-known hydrophobic porous coordination polymer. Owing to the hydrophobic ethyl radical on the surface of its pore channel, it does not adsorb water vapor basically at room temperature and its structure can be stable in air and water. It can adsorb various solvents including methanol, ethanol, acetonitrile and benzene, can be used for separation of organic solvents and water, and exhibits dynamic response phenomenon (structural change) to various guest molecules due to the flexibility of MAF-2 structure. Since the dynamic ethyl stops at the position of the window, it exhibits special flexibility and gas adsorption properties. For example, it adsorbs nitrogen at 195K rather than 77K. It can also adsorb benzene but not cyclohexane, and can be used for separating benzene and cyclohexane. However, MAF-2 is oxidized on the crystal surface in humid air, indicating that there is room for improvement in stability.
Disclosure of Invention
The invention aims to solve the technical problem that the stability of the existing hydrophobic porous coordination polymer in humid air needs to be further improved (such as MAF-2), and provides a class of super-hydrophobic porous coordination polymer based on a part of fluoro organic ligands, wherein 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole is used as a ligand, and two new examples of porous coordination polymers are constructed with silver ions or monovalent copper ions, and the codes are MAF-9 and MAF-2F respectively. The super-hydrophobic porous coordination polymers can adsorb methanol, ethanol and benzene vapor, basically do not adsorb water, have good thermal stability and solvent stability, are particularly easy to synthesize, and have a certain application prospect.
Another object of the present invention is to provide a method for preparing a class of superhydrophobic porous coordination polymers based on partially fluorinated organic ligands.
It is a further object of the present invention to provide a class of superhydrophobic, porous coordination polymers based on partially fluorinated organic ligands.
The above purpose of the invention is realized by the following technical scheme:
a super-hydrophobic porous coordination polymer based on a part of fluoro organic ligand is formed by assembling after all nitrogen atoms of 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anions are coordinated with silver ions or monovalent copper ions.
The two super-hydrophobic porous coordination polymers MAF-9 and MAF-2F have available pore channels, the pore rate is 38% -41%, trifluoromethyl and ethyl on a ligand in the structure are exposed on the surface of the pore channels, and the ethyl and the trifluoromethyl are hydrophobic functional groups, so that the surface of the material has hydrophobic and oleophilic properties. Due to the hydrophobicity of the surface of the porous material, the porous material has strong affinity to organic solvents (oiliness), completely repels water molecules, basically does not adsorb water at room temperature, can adsorb equivalent organic molecules such as benzene series, methanol, ethanol and the like, and also has good chemical and thermal stability.
One of the super-hydrophobic porous coordination polymers is MAF-9 which is constructed by silver ions and 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole. Further, the metal ions are silver ions, and the chemical formula of the super-hydrophobic porous coordination polymer MAF-9 is [ Ag (fetz) ]]Therein fetz-Representing organic ligand 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anion, the super-hydrophobic porous coordination polymer is crystallized in a tetragonal system, the space group is I-42d, and the unit cell parameter is
Cell volume
The super-hydrophobic porous coordination polymer is prepared from fitz-All nitrogen atoms and silver ions are assembled into the super-hydrophobic porous coordination polymer with three-dimensional pore passages which are mutually penetrated through a complex coordination mode. Wherein MAF-9 has a pore size of
The void fraction was 41%. The hydrophobic functional groups trifluoromethyl and ethyl on the ligand are exposed on the surface of the pore channel, the metal ions and coordination bonds are completely blocked, and the material is super-hydrophobic.
Wherein the 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole has a molecular structure shown in formula (I), and the structural formula is as follows:
another hydrophobic porous coordination polymer in the present invention is MAF-2F. Go toThe metal ions are monovalent copper ions, and the chemical formula of the super-hydrophobic porous coordination polymer is [ Cu (ftz) ]]Therein fetz-Representing organic ligand 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anion, the super-hydrophobic porous coordination polymer is crystallized in a trigonal system, the space group is R-3, and the unit cell parameter is
Cell volume
The super-hydrophobic porous coordination polymer is prepared from fitz-All nitrogen atoms and monovalent copper ions are assembled into the super-hydrophobic porous coordination polymer with a three-dimensional structure through coordination bonds. MAF-2F has one-dimensional cage-shaped holes with a porosity of 38.3% and a cage diameter of
Window diameter of
The invention protects the preparation method of the MAF-9 of the super-hydrophobic porous coordination polymer, which comprises the following steps:
silver nitrate and 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand in a molar ratio of 1: 1-5 are respectively dissolved in water and methanol, a benzene series solvent is used as an intermediate layer, and a super-hydrophobic porous coordination polymer (MAF-9) is prepared by a diffusion method. The product is MAF-9 single crystal.
Preferably, the molar ratio of the silver nitrate to the 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole (Hfetz) is 1: 1-3.
Preferably, silver nitrate is added, a benzene series solvent is added to serve as a middle layer, and finally 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand is added, standing is carried out for 10-14 days, and the super-hydrophobic porous coordination polymer is prepared after filtering, washing and drying.
Preferably, the benzene series solvent used in the middle layer is one or more than two of mesitylene, o-xylene, p-xylene, m-xylene, benzene or toluene.
The invention protects the preparation method of the super-hydrophobic porous coordination polymer MAF-9, which comprises the following steps:
firstly, respectively preparing an organic solvent solution of 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand and a silver nitrate aqueous solution, uniformly mixing the two solutions, reacting for 2-4 h at 25-30 ℃, filtering, washing and drying to obtain a super-hydrophobic porous coordination polymer powder sample.
Further, the concentration of the organic solvent solution of the 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand is 0.02-0.1 mol/L.
Further, the concentration of the silver nitrate water solution is 0.02-0.1 mol/L.
Further, the organic solvent is one or more than two of benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, chloroform or dichloromethane.
The invention protects the preparation method of the super-hydrophobic porous coordination polymer MAF-2F, which comprises the following steps:
respectively dissolving copper nitrate and 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand in a molar ratio of 1: 1-5 in water and an organic solvent, mixing, reacting at 100-160 ℃ for 72-80 h under a closed condition, and cooling to obtain the super-hydrophobic porous coordination polymer 3-ethyl-5-trifluoromethyl-cuprous triazole (MAF-2F). MAF-2F single crystal samples were prepared.
Preferably, the molar ratio of the copper nitrate to the 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole is 1: 1-3.
Preferably, the organic solvent is one or more than two of mesitylene, p-xylene, o-xylene, m-xylene, toluene, benzene or chloroform.
The invention protects the preparation method of the super-hydrophobic porous coordination polymer MAF-2F, which comprises the following steps:
dissolving nano cuprous oxide in an organic solvent, adding 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand in an inert atmosphere, uniformly mixing, reacting at 50-80 ℃ for 0.5-5 h, filtering, washing and drying to obtain a super-hydrophobic porous coordination polymer powder sample, wherein the molar ratio of the nano cuprous oxide to the 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand is 1:1 to 3.
The specific preparation method of the porous coordination polymer MAF-2F comprises the following steps:
ultrasonically dispersing nano cuprous oxide in ethanol, adding Hfetz ligand under the protection of nitrogen, quickly sealing, mixing and stirring uniformly, heating and refluxing at 80 ℃ for 30min, and filtering, washing and drying to obtain the MAF-2F powder sample.
Generally speaking, the synthesis method of the single crystal sample has low yield, is suitable for single crystal X-ray diffraction experiments to test accurate crystal structures, and has small sample consumption. However, the synthesis method of the single crystal sample is not suitable for amplification and is therefore not suitable for property tests with large using amount of other samples, and the preparation method of the powder sample is suitable for mass preparation and can be used for production or other property tests. The two preparation methods produce products with completely identical structures.
Preferably, the preparation method of the 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole (Hfetz) ligand comprises the following steps:
adding ethyl trifluoroacetate and hydrazine hydrate into tetrahydrofuran, and reacting for 2-5 h at 90-100 ℃; cooling to 25-30 ℃, adding propamidine hydrochloride and NaOH, reacting for 4-6 h at 90-100 ℃, then quenching in a saturated sodium bicarbonate aqueous solution at 0 ℃, adjusting the pH to 8-9, extracting and drying to obtain a 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand; wherein the molar ratio of ethyl trifluoroacetate to hydrazine hydrate to propamidine hydrochloride to NaOH is 45-55: 40-55: 40-55: 40 to 55.
Further, the extraction and drying operations are as follows: extracting with ethyl acetate, adding excessive anhydrous sodium sulfate for dehydration, spin-drying the solvent at 50-60 ℃, and subliming.
The invention also protects the application of the super-hydrophobic porous coordination polymer in preparing self-cleaning film materials and/or self-cleaning surfaces and serving as a heterogeneous catalyst.
The invention also protects the application of the super-hydrophobic porous coordination polymer in oil-water separation and gas adsorption separation.
The two super-hydrophobic porous coordination polymers have good stability, can adsorb equivalent organic vapor such as benzene series, methanol, ethanol and the like, and can be used for separating volatile organic matters from water without adsorbing water.
Compared with the prior art, the invention has the beneficial effects that:
the invention designs a super-hydrophobic porous coordination polymer with a three-dimensional structure, which is formed by assembling 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anions and silver ions or monovalent copper ions after coordination.
(1) The preparation method of the super-hydrophobic porous coordination polymers MAF-9 and MAF-2F is very simple, the single crystal preparation method is suitable for single crystal X-ray diffraction experiments, and the powder preparation method is suitable for large-scale synthesis. Compared with the complicated synthesis steps of FMOF-1, the single crystal sample preparation method of MAF-9 can be prepared by stirring at room temperature in a simple step, and the synthesis method of MAF-2F is simpler than that of MAF-2.
(2) The super-hydrophobic porous coordination polymer MAF-9 and MAF-2F has good structural chemistry and thermal stability; wherein the stability of MAF-2F is greatly improved compared with that of MAF-2.
(3) The super-hydrophobic porous coordination polymers MAF-9 and MAF-2F are both super-hydrophobic structures, do not absorb water basically at room temperature, can absorb equivalent amounts of benzene series, methanol, ethanol and other organic vapor, and can be used for separating volatile organic matters from water.
(4) The mass adsorption amount of low-temperature nitrogen of MAF-9 is 16% higher than that of FMOF-1, and the low-temperature CO of MAF-2F2The volumetric adsorption was also 25% higher than MAF-2.
Drawings
FIG. 1 is a molecular structure diagram of 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole (Hfetz) ligand of the invention.
FIG. 2 is a graph of the structure and channels of a MAF-9 of the present invention.
FIG. 3 is an X-ray powder diffraction pattern of MAF-9 obtained in example 1 of the present invention.
FIG. 4 is a graph of the stability of MAF-9 prepared in example 1 of the present invention in various solvents.
FIG. 5 is a thermogravimetric plot of MAF-9 made in example 1 of the invention.
FIG. 6 is a nitrogen adsorption isotherm at 77K for MAF-9 prepared in example 1 of the present invention.
FIG. 7 is a graph of the vapor sorption isotherms of water, methanol, ethanol and benzene at 298K for MAF-9 prepared in example 1 of the present invention.
FIG. 8 is a photograph showing the water contact angle of MAF-9 obtained in example 1 of the present invention.
FIG. 9 is a block diagram of MAF-2F according to the present invention.
FIG. 10 is an X-ray powder diffraction pattern of MAF-2F obtained in example 3 of the present invention.
FIG. 11 is a thermogravimetric plot of MAF-2F prepared in example 3 of the present invention.
FIG. 12 is a graph of the stability of MAF-2F prepared in example 3 of the present invention in different solvents.
FIG. 13 is a 77K nitrogen adsorption isotherm for MAF-2F prepared in example 3 of the invention.
FIG. 14 is a graph of the vapor sorption isotherms of water, methanol, ethanol and benzene at 298K for MAF-2F prepared in example 3 of the present invention.
FIG. 15 is a photograph showing the water contact angle of MAF-2F obtained in example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the examples are not intended to limit the invention in any manner unless otherwise specified. The raw material reagents adopted in the embodiment of the invention are purchased from conventional reagent suppliers and are directly used without purification.
Example 1
A super-hydrophobic porous coordination polymer (MAF-9) based on a part of fluoro organic ligand is formed by assembling after all nitrogen atoms of 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anions are coordinated with silver ions.
The preparation method of the single crystal of the MAF-9 comprises the following steps:
preparation of organic ligand Hfetz
Adding ethyl trifluoroacetate and hydrazine hydrate into tetrahydrofuran, heating to 90 ℃ for reflux reaction for 2 hours, cooling to 25 ℃, then adding propionamidine hydrochloride and NaOH, heating to 90 ℃ for reflux reaction for 4 hours; quenching the reacted liquid in a saturated sodium bicarbonate aqueous solution at 0 ℃, adjusting the pH value to 8 by using sodium bicarbonate, extracting for three times by using ethyl acetate, adding excessive anhydrous sodium sulfate into an organic phase after extraction for dehydration, and carrying out spin-drying at 50 ℃ on a solvent for sublimation to finally obtain a white crystalline solid, namely a ligand 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole (Hfetz), wherein the yield is 88%; wherein the molar ratio of ethyl trifluoroacetate, hydrazine hydrate, propamidine hydrochloride to NaOH is 50: 50: 55: 55.
preparation of super-hydrophobic porous coordination polymer MAF-9 single crystal
Adding silver nitrate aqueous solution into a test tube, slowly adding toluene as an intermediate layer, and finally adding the prepared methanol solution of the Hfetz ligand at the upper layer, wherein the molar ratio of silver nitrate to Hfetz is 1:1, standing for 14 days to obtain colorless rectangular blocky single crystal MAF-9 with the yield of 50%.
EXAMPLE 2 MAF-9 powder sample preparation method
The ligand Hfetz was prepared in the same manner as in example 1.
Firstly, respectively preparing a toluene solution of Hfetz and a silver nitrate aqueous solution, slowly mixing the two solutions uniformly, reacting for 2 hours at room temperature, and filtering, washing and drying to obtain a white MAF-9 powder sample, wherein the molar ratio of silver nitrate to Hfetz is 1:1, and the yield reaches 65%.
EXAMPLE 3 MAF-2F Single Crystal production method
A super-hydrophobic porous coordination polymer (MAF-2F) based on a part of fluoro organic ligand is formed by assembling all nitrogen atoms of 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anions and monovalent copper ions after coordination.
The preparation method of the MAF-2F comprises the following steps:
wherein the ligand Hfetz was prepared in the same manner as in example 1.
First Cu (NO)3)2And Hfetz ligand in water and toluene, respectively, with Cu (NO)3)2And Hfetz ligand in a molar ratio of 1:1, mixing the two solutions, stirring uniformly, sealing in a stainless steel reaction vessel with a polytetrafluoroethylene lining, heating to react at 160 ℃ for 72h, and cooling to room temperature at a speed of 5 ℃/h to obtain a colorless block MAF-2F sample with a yield of about 80%.
EXAMPLE 4 MAF-2F powder sample preparation method
The ligand Hfetz was prepared in the same manner as in example 1.
Ultrasonically dispersing nano cuprous oxide in ethanol, adding Hfetz ligand under the protection of nitrogen, quickly sealing, mixing and stirring uniformly, heating and refluxing at 80 ℃ for 30min, and filtering, washing and drying to obtain the MAF-2F powder sample, wherein the yield reaches 96%.
Comparative example 1
Reacting sodium salt of bis (trifluoromethyl) -1,2, 4-triazole with silver nitrate at room temperature, and performing multiple operations such as volatilization, recrystallization and the like to obtain the porous coordination polymer FMOF-1. Wherein the sodium salt of bis (trifluoromethyl) -1,2, 4-triazole can be prepared by multi-step reactions such as condensation, halogenation, amination, ring closure and the like.
Comparative example 2
Firstly, preparing a copper ammonia solvent with a certain concentration, reducing the copper ammonia solvent into monovalent copper by hydrazine hydrate under the protection of nitrogen, then gradually dropwise adding a methanol solution of 3, 5-diethyl-1, 2, 4-triazole, wherein the ratio of a ligand to metal ions is 1: 1-1.1, stirring for 5 hours at room temperature, filtering, and washing to obtain a white powder sample which is a coordination polymer MAF-2.
Performance testing
1. Test method
(1) The single crystal structure parameters are as follows: single crystal diffraction data were collected on a Rigaku Oxford SuperNova single crystal instrument.
(2) And (3) thermal stability characterization: obtained by thermogravimetric analysis, 10 ℃ on a TA Q50 thermogravimetric instrumentmin-1Heating to over 500 deg.c to obtain thermogravimetric graph.
(3) Characterization of gas adsorption properties: putting the super-hydrophobic porous coordination polymer into a glass sample tube, vacuumizing and heating, and measuring a low-temperature nitrogen adsorption isotherm by using an ASAP 2020M adsorption instrument under the condition of 77K. N of MAF-9 and MAF-2F2The adsorption isotherms are all type I adsorption isotherms.
(4) Characterization of different vapor adsorption properties: the MAF-9 prepared in example 1 and the MAF-2F prepared in example 3 were placed in glass sample tubes, respectively, activated by heating at 110 ℃ for 2 hours under a high vacuum (0.5Pa), cooled to room temperature, and then the adsorption test was started. And then measuring different vapor adsorption isotherms of the sample under the condition of a BEL max adsorption instrument 298K (circulating water bath temperature control). Vapor adsorption isotherms of methanol, ethanol, benzene, cyclohexane and water were obtained.
(5) MAF-9 Water contact Angle test method: samples of MAF-9 (about 100mg) obtained in example 1 and MAF-2F (about 100mg) obtained in example 3 were each pressed flat on a glass plate, and then a drop of about 4 to 8. mu.l was dropped on the flat surface, and photographed on a water contact angle meter to obtain a water contact angle photograph.
2. Test results
TABLE 1 Crystal Structure parameters of MAF-9 and FMOF-1
Table 1 shows the parameters of single crystal structure of MAF-9. FIG. 2 is a graph of the pore path of MAF-9, the stoichiometric ratio of silver ions to Hfetz ligand in the MAF-9 independent structural unit is 1:1, and the chemical formula is [ Ag (fetz)]. Three nitrogen atoms on the Hfetz ligand are all involved in coordination, silver ions are in three-coordination and four-coordination modes, and are assembled into a three-dimensional framework through coordination bonds with the ligand; MAF-9 has three-dimensional pores with interpenetration along the a-axis and b-axis, pore size ranging from
The coordination polymer prepared by the method is compared with the coordination polymer prepared by comparative example 1 because of dynamic ethyl on the surface of the pore channelCompound FMOF-1 has a larger size range. The MAF-9 porosity was 41.0%, which was equivalent to that of the coordination polymer FMOF-1 prepared in comparative example 1 (FMOF-1 porosity was 44.4%), wherein the porosity, as calculated by Platon software, was determined by default as the molecular radius of the probe
FIG. 1 is a molecular structure diagram of Hfetz ligand, wherein trifluoromethyl and ethyl on the ligand are exposed on the surface of the super-hydrophobic porous coordination polymer pore channel, so that the material shows super-hydrophobicity.
FIG. 2 shows MAF-9 intersecting columnar cells along the a-axis and b-axis.
As can be seen in FIG. 3, the original synthesized powder diffraction peak of MAF-9 can be completely correlated with the simulated MAF-9, demonstrating that the synthesized sample is phase pure.
FIG. 4 shows the stability of MAF-9 in different solvents, and it can be seen from the graph that MAF-9 can be stabilized in boiling water for a certain period of time and in humid air for one year by heating in alcohol and benzene solvents for a long time, thus proving that the solvent stability of MAF-9 is good.
As can be seen from the thermogravimetric plot of FIG. 5, MAF-9 was stable to 280 ℃ and the thermal stability was comparable to that of the coordination polymer FMOF-1(280 ℃) obtained in comparative example 1.
TABLE 2 comparison of porosity of MAF-9 and FMOF-1
Table 2 shows that the pore size of MAF-9 is slightly smaller than that of FMOF-1, but the pore volume is comparable to that of FMOF-1. Since the ethyl molecular weight is less than that of trifluoromethyl, the MAF-9 density is less. As can be seen from the nitrogen adsorption isotherm of MAF-9 at 77K in FIG. 6, the low-temperature nitrogen adsorption amount of MAF-9 reached 10.97mmol/g (10.97mmol/g is 245.7 cm)3/g) higher than FMOF-1 by 16%, the low temperature nitrogen adsorption behavior of MAF-9 is similar to that of FMOF-1, but since the density of MAF-9 is lower than that of FMOF-1, the low temperature nitrogen adsorption of MAF-9 and FMOF-1, both of which are of the same mass, is higher. Wherein the abscissa of fig. 6Is relative pressure, P/P0Wherein P is the equilibrium pressure, P0Is the saturated vapor pressure. The solid and hollow curves with the same shape respectively correspond to the adsorption and desorption curves of the same substance.
FIG. 7 is a vapor adsorption isotherm of room temperature water, methanol, ethanol and benzene of MAF-9 of the present invention, in which the adsorption amounts of MAF-9 to methanol, ethanol and benzene vapor are 5.0, 3.3 and 2.4mmol/g, respectively, and the adsorption amount of benzene vapor is 7% higher than that of FMOF-1 (the adsorption amount of benzene vapor of FMOF-1 is 2.23 mmol/g). Even at high humidity (P/P)00.99, saturated vapor pressure at a temperature close to water temperature), MAF-9 also had a water vapor adsorption amount of only 0.07mmol/g, and almost no water was adsorbed. The test of the steam adsorption isotherm further verifies the oleophylic and hydrophobic characteristics of MAF-9, and shows that the MAF-9 has application potential in the field of oil-water separation. The abscissa of fig. 7 is the relative pressure, as in fig. 6. The solid and hollow curves with the same shape respectively correspond to the adsorption and desorption curves of the same substance.
FIG. 8 is a photograph showing the water contact angle of MAF-9 of the present invention, which is as high as 152 degrees, and is an example of a super-hydrophobic porous material (the water contact angle is larger than 150 degrees, i.e., the super-hydrophobic material), which has a water contact angle close to that of FMOF-1 (the water contact angle of FMOF-1 is 158 degrees). The novel super-hydrophobic porous coordination polymer MAF-9 has excellent surface hydrophobicity, and can be used as a preferred material for preparing self-cleaning coatings and/or surfaces.
TABLE 3 Crystal Structure parameters for MAF-2F
Table 3 shows the parameters of single crystal structure of MAF-2F. FIG. 9 is a schematic diagram of MAF-2F. MAF-2F and MAF-2 are completely homogeneous. The porosity of MAF-2F was 38.3%, which was 22% higher than that of MAF-2 (the porosity of MAF-2 was 31.3%), wherein the porosity was calculated by the Platon software.
FIG. 10 is a powder diffraction pattern of MAF-2F according to the present invention, wherein the original synthesized X-ray powder diffraction pattern can be well matched with the simulation, thus proving that the purity of the synthesized sample is high.
FIG. 11 is a thermogravimetric plot of MAF-2F according to the present invention, MAF-2F has a better thermogravimetric plateau, stable to 280 ℃ and thermal stability comparable to MAF-2 (stable to 280 ℃).
FIG. 12 shows the stability of MAF-2F in different solvents, the structure of which is maintained even when heated for a long time in boiling alcohol and benzene solvents, and the stability of which is maintained for a certain time in boiling water. Because the hydrophobicity of the MAF-2F is high, the sample can keep white after being placed in humid air for more than 3 months, and the stability is obviously improved compared with the MAF-2. In general, a porous coordination polymer with good stability can be stable in humid air, while a porous coordination polymer with poor stability can only be stable in a specific solvent, and the structure is completely destroyed when the porous coordination polymer is in contact with air or humid air. For example, MAF-2 is oxidized on the crystal surface after being left in humid air for 1 month, and the white crystal surface turns green.
TABLE 4 porosity of MAF-2F and MAF-2
Table 4 shows that the hole rate of MAF-2F is significantly higher than MAF-2, and cage size is comparable to MAF-2. MAF-2F adsorbs nitrogen at 77K because nitrogen molecules can enter the cage through six trifluoromethyl windows aligned along the c-axis, whereas MAF-2 blocks the windows due to the dynamic ethyl groups and does not adsorb nitrogen substantially at 77K. In addition, the volume adsorption amount of 195K carbon dioxide of MAF-2F is 25% higher than that of MAF-2, and the mass adsorption amount is 6% higher than that of MAF-2.
FIG. 13 is a nitrogen adsorption isotherm of MAF-2F at 77K according to the present invention, wherein the low temperature nitrogen isotherm of MAF-2F is of type I, the adsorption amount can reach 8.0mmol/g, and the adsorption amount is substantially consistent with the theoretical adsorption amount. MAF-2F adsorption behavior is significantly different from MAF-2, which does not adsorb nitrogen at 77K due to the dynamic ethyl blocking the window completely. Wherein the abscissa of FIG. 13 is the relative pressure, P/P0Wherein P is the equilibrium pressure, P0Is the saturated vapor pressure. The solid and hollow curves with the same shape respectively correspond to the adsorption and desorption curves of the same substance.
FIG. 14 shows the room temperature vapor adsorption of MAF-2F according to the present inventionThe adsorption amounts of methanol, ethanol and benzene vapor at room temperature of the temperature line, MAF-2F were 4.87, 4.36 and 2.12mmol/g, respectively, while water vapor was hardly adsorbed at all. Wherein the abscissa of FIG. 14 is relative pressure, P/P0Wherein P is the equilibrium pressure, P0Is the saturated vapor pressure. The solid and hollow curves with the same shape respectively correspond to the adsorption and desorption curves of the same substance.
FIG. 15 is a photograph of water contact angle of MAF-2F according to the present invention, wherein the water contact angle is as high as 152 degrees, which is an example of a super-hydrophobic porous material (the water contact angle is larger than 150 degrees, i.e. the super-hydrophobic material), and is higher than the water contact angle (140 degrees) of MAF-2, which shows that the trifluoromethyl group in MAF-2F significantly increases the hydrophobicity of MAF-2F.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (8)
1. A super-hydrophobic porous coordination polymer based on a part of fluoro organic ligand is characterized in that after all nitrogen atoms of 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anions are coordinated with silver ions or monovalent copper ions, the super-hydrophobic porous coordination polymer with a three-dimensional structure is assembled;
when the silver ion is contained, the chemical formula of the super-hydrophobic porous coordination polymer is [ Ag (fetz) ]]Therein fetz-Representing organic ligand 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anion, the super-hydrophobic porous coordination polymer is crystallized in a tetragonal system, the space group is I-42d, and the unit cell parameter is
Cell volume
The super-hydrophobic porous coordination polymer is prepared from fitz-All nitrogen atoms and silver ions are assembled into a super-hydrophobic porous coordination polymer with a three-dimensional pore channel structure through a complex coordination mode;
when the copper ions are monovalent, the chemical formula of the super-hydrophobic porous coordination polymer is [ Cu (ftz) ]]Therein fetz-Representing organic ligand 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole anion, the super-hydrophobic porous coordination polymer is crystallized in a trigonal system, the space group is R-3, and the unit cell parameter is
Cell volume
The super-hydrophobic porous coordination polymer is prepared from fitz-All nitrogen atoms and monovalent copper ions are assembled into the super-hydrophobic porous coordination polymer with a three-dimensional structure through coordination bonds.
2. The method of preparing a superhydrophobic porous coordination polymer of claim 1, comprising the steps of:
silver nitrate and 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand in a molar ratio of 1: 1-5 are respectively dissolved in water and methanol, a benzene series solvent is used as an intermediate layer, and the super-hydrophobic porous coordination polymer is prepared by a diffusion method.
3. A method for preparing the superhydrophobic porous coordination polymer of claim 1, comprising the steps of:
firstly, respectively preparing an organic solvent solution of 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand and a silver nitrate aqueous solution, uniformly mixing the two solutions, reacting for 2-4 h at 25-30 ℃, filtering, washing and drying to obtain a super-hydrophobic porous coordination polymer powder sample.
4. The method of preparing a superhydrophobic porous coordination polymer of claim 1, comprising the steps of:
respectively dissolving copper nitrate and 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand in a molar ratio of 1: 1-5 in water and an organic solvent, mixing, reacting at 100-160 ℃ for 72-80 h under a closed condition, and cooling to obtain the super-hydrophobic porous coordination polymer 3-ethyl-5-trifluoromethyl-cuprous triazole.
5. The method of preparing a superhydrophobic porous coordination polymer of claim 1, comprising the steps of:
dissolving nano cuprous oxide in an organic solvent, adding 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand in an inert atmosphere, uniformly mixing, reacting at 50-80 ℃ for 0.5-5 h, filtering, washing and drying to obtain a super-hydrophobic porous coordination polymer powder sample, wherein the molar ratio of the nano cuprous oxide to the 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand is 1:1 to 3.
6. The preparation method of any one of claims 2 to 5, wherein the preparation method of the 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand comprises the following steps:
adding ethyl trifluoroacetate and hydrazine hydrate into tetrahydrofuran, and reacting for 2-5 h at 90-100 ℃; cooling to 25-30 ℃, adding propamidine hydrochloride and NaOH, reacting for 4-6 h at 90-100 ℃, then quenching in a saturated sodium bicarbonate aqueous solution at 0 ℃, adjusting the pH to 8-9, extracting and drying to obtain a 3-ethyl-5-trifluoromethyl-1, 2, 4-triazole ligand; wherein the molar ratio of ethyl trifluoroacetate to hydrazine hydrate to propamidine hydrochloride to NaOH is 45-55: 40-55: 40-55: 40 to 55.
7. Use of the superhydrophobic porous coordination polymer of claim 1 in the preparation of self-cleaning thin film materials and/or self-cleaning surfaces and as a heterogeneous catalyst.
8. The use of the superhydrophobic porous coordination polymer of claim 1 in oil-water separation and gas adsorption separation.
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| "Partially Fluorinated Cu(I) Triazolate Frameworks with High Hydrophobicity, Porosity, and Luminescence Sensitivity";Chao Wang et al.;《Inorg. Chem.》;20190305;第58卷;第3944-3949页 * |
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